Detailed Information on Publication Record
2017
In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups
SLANINA, Tomáš, Pradeep SHRESTHA, Eduardo PALAO UTIEL, Dnyaneshwar KAND, Julie A. PETERSON et. al.Basic information
Original name
In Search of the Perfect Photocage: Structure Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups
Authors
SLANINA, Tomáš (203 Czech Republic, belonging to the institution), Pradeep SHRESTHA (840 United States of America), Eduardo PALAO UTIEL (724 Spain, belonging to the institution), Dnyaneshwar KAND (376 Israel), Julie A. PETERSON (840 United States of America), Andrew S. DUTTON (840 United States of America), Naama RUBINSTEIN (376 Israel), Roy WEINSTAIN (376 Israel), Arthur H. WINTER (840 United States of America) and Petr KLÁN (203 Czech Republic, guarantor, belonging to the institution)
Edition
Journal of the American Chemical Society, WASHINGTON, American Chemical Society, 2017, 0002-7863
Other information
Language
English
Type of outcome
Článek v odborném periodiku
Field of Study
10400 1.4 Chemical sciences
Country of publisher
United States of America
Confidentiality degree
není předmětem státního či obchodního tajemství
Impact factor
Impact factor: 14.357
RIV identification code
RIV/00216224:14310/17:00099992
Organization unit
Faculty of Science
UT WoS
000414115800052
Keywords in English
P-HYDROXYPHENACYL; VISIBLE-LIGHT; CAGED GABA; REACTION-MECHANISMS; STOKES SHIFT; GREEN LIGHT; DYES; DERIVATIVES; ATP; PHOTOCHEMISTRY
Tags
International impact, Reviewed
Změněno: 5/4/2018 13:55, Ing. Nicole Zrilić
Abstract
V originále
A detailed investigation of the photophysical parameters and photochemical reactivity of meso-methyl BODIPY photoremovable protecting groups was accomplished through systematic variation of the leaving group (LG) and core substituents as well as substitutions at boron. Efficiencies of the LG release were evaluated using both steady-state and transient absorption spectroscopies as well as computational analyses to identify the optimal structural features. We find that the quantum yields for photorelease with this photocage are highly sensitive to substituent effects. In particular, we find that the quantum yields of photorelease are improved with derivatives with higher intersystem crossing quantum yields, which can be promoted by core heavy atoms. Moreover, release quantum yields are dramatically improved by boron alkylation, whereas alkylation in the meso-methyl position has no effect. Better LGs are released considerably more efficiently than poorer LGs. We find that these substituent effects are additive, for example, a 2,6-diiodo-B-dimethyl BODIPY photocage features quantum yields of 28% for the mediocre LG acetate and a 95% quantum yield of release for chloride. The high chemical and quantum yields combined with the outstanding absorption properties of BODIPY dyes lead to photocages with uncaging cross sections over 10 000 M-1 cm(-1), values that surpass cross sections of related photocages absorbing visible light. These new photo cages, which absorb strongly near the second harmonic of an Nd:YAG laser (532 nm), hold promise for manipulating and interrogating biological and material systems with the high spatiotemporal control provided by pulsed laser irradiation, while avoiding the phototoxicity problems encountered with many UV-absorbing photocages. More generally, the insights gained from this structure reactivity relationship may aid in the development of new highly efficient photoreactions.
Links
| LM2011028, research and development project |
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| LO1214, research and development project |
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